Vat dyestuff of the anthraquinone series



Patented May 7, 1935 UNITED STATES PATENT OFFICE.

VAT DYESTUFF OF T Heinrich N eresheimer,

HE ANTHRAQUINONE RIES Wilhelm Ruppel, and

Anton Vilsmeier, Ludwigshafen-on-the-Rhine,

Germany, assignors to Inc., New York, N. Y.,

ware

General Aniline Works, a corporation of Dela- No Drawing. Application June 2 0, 1932, Serial No. 618,342. In Germany June 25, 1931 7 Claims.

Dyestuffs which are derived on the one hand from 1,2-benzanthraquinone-Bz4-carboxylic acid and on the other hand from 1,5- or 1,8 diaminoanthraquinones are especially valuable. The preparation of the said dyestuffs may be effected by difierent methods. Thus for example one and the same yellow dyestuff very fast to light is obtained by causing 2 molecular proportions of 1,2-benzanthraquinone Bz4-carboxylic acid chloride to react with 1 molecular proportion of 1,5-diaminoanthraquinone, or 2 molecular proportions of 1,2 benzanthraqulnone-Ba4=-carboxylic acid amide with 1 molecular proportion of 1,5-dichloranthraquinone, or 1 molecular proportion of 1-amino-(1,2 benzanthraquinone-Bzt carboxyl) -5-aminoanthraquinone with 1, molecular proportion of 1,2-benzanthraquinone-Bz4- carboxylic acid chloride or 1 molecular proportion of l-chlor- (1,2-benzanthraquinone-Bz4-carboxyl)-5-aminoanthraquinone with 1 molecular proportion of .1,2-benzanthraquinone-Bz4-carboxylic acid amide. The latter compound may be prepared by saponifying Bz4-cyan-L2-benzanthraquinone by means of 96 per cent sulphuric acid at about 90 C.

The dyestuffs in which only one amino group of the 1,5- or 1,8-diaminoanthraquinone bears the l,2-benzanthraquinone-Bz4-carboxylic acid radicle while the other amino group is acylated by another acid radicle havingsimilar valuable properties.

The following examples will further illustrate the nature of this invention but the invention is not restricted to these examples. The parts' are by weight.

Example 1 1 part of -1-amino5-benzoylaminoanthraquinoneis heated with 1,2 parts of 1,2-benzanthraquinone'-Bzl-carboxylic acid chloride (prepared from Bz4-brom-1,2-benzanthraquinone by conversion into B24-cyan-1,2-benzanthraquinone by means of cuprous cyanide, saponification of the nitrile and treatment of the carboxylic acid with thionyl chloride, the resulting carboxylic acid chloride crystallizing from ortho-dichlorbenzene in the form of olive yellow needles) slowly to about 200 C. in 20 parts of nitrobenzene and kept at the said temperature until the formation 7 of dyestufi is completed. The dyestuff separates in the form of a pale brown crystalline powder and forms yellow needles when crystallized from nitrobenzene. It dyes cotton very fast clearyellow shades from a yellowish red vat.

If the 1,2-benzanthraquinone-Bz4-carboxylic acid chloride be replaced by 6-chlor-l,2-benzanthraquinone-Bz4-carboxylic acid chloride prepared in an analogous manner from 6-chlorBz4- brom 1,2 benzanthraquinone (obtainable by brominating G-chlor-1,2-benzanthraquinone and crystallizing in the form of yellow needles from nitrobenzene), a dyestufi which is very similar to that already described is obtained.

Erample 2 at the said temperature until the formation of dyestuff is completed. The separating dyestufi is identical with that obtained according to Example 1.

Example 3 lpart of 1,5-diaminoanthraquinone and 3.5 parts of 1,2-benzanthraquinone-Bz4-carboxylic acid chloride are slowly heated to boiling in 45 parts of nitrobenzene and the reaction mixture is kept at the boiling temperature for 5 hours;

Other solvents of high boiling point, as for example naphthalene or diphenyl ether may be employed instead of nitrobenzene.

By starting from 1,8-diaminoanthraquinone instead of from1.5-diaminoanthraquinone a very similar dyestvfi is obtained.

Example 4 -1 part of 1,5-dichloranthraquinone; 2.5.parts.

1,2 benzanthraquinone B24 carboxylic a c i d amide, 1 part of anhydrous potash, 0.1 7 part of copper powder and 0.17 part. otcopper acetate are heated to 240 C. for several hours in 45 parts;

of alpha-nitronaphthalene. After. cooling, the reaction mixture is diluted with ethyl alcohol. The dyestuft is freed from more readily soluble lay-products, when necessary; :by boiling with glacial acetic acid. It is identical with" the dyestuii obtained according to Example-v 3..

Example. 5-.

11 part; of l-ohlo1&5 benzoylaminoanthraquinone, 1 part ofv 1,2-benzanthraquinone-Bz4-carboxylic acid an1ide,.i).45 part of potash, 0.07 part i of. copper powder and 0.07 part of copper acetate are heatedto 240 C. in 25 parts otdiphenyl ether 7 for several hours and then worked up as described in; Example 4. The dyestuff is identical with that prepared according to Example 1.

Example 6 1 part of .l-aminoanthraquinone is slowly heated to 190 to 200 C. in 30 parts, of nitroben: zene with 1.42. parts of 1,2-benzanthraquinone- Bzdecarboxylic acid chloride, the reaction mixture being kept at the said. temperature until; the formation of the dyestuff is complete. The reaction product is worked up in' the usual manner. It dyes cotton from a yellowish red vat "greenish yellow shades.

Example 7 1.42- parts of 1,2i-benzanthraquinone-Bz-carboxy-lie acid chloride. (which is obtainable'bycondensing, .fl-naphthonitrile with phthalic: an-

hydride ,.saponifying the obtainedl,2.-benzanthra-- quinone-Bz-nitrile with sulphuric acid: and con: verting the formed carboxylic acid in a known v manner into the acid chloride", and which is consid ered. to be l .,2-benzanthraquinone-Bz-2-carboxylic; acid chloride or 1.2-benzanthraquinone- Bz-3-carboxylio acid chloride) are heated with: 1 part of -aminoanthraquinone in 30 parts of nitrobenzene up to 130 C. which temperature is maintained until the formation of. the dyestuff is completed. The latter isworked up in the usual manner. it dyes greenish yellow shades.

Example 8 1.2 parts of 1,2-benzanthraquinone-Bz-carboxylic acid chloride (obtained in the manner described in Example 7) are slowly heated together with 1 part of 1amino-5-benzoylaminoanthraquinone in 25 parts of nitrobenzene up to 140 C. which temperature is maintained until the for; mation of the dyestuif 15' complete. The latter is worked up in the. usual manner. It forms a red vat from. which it dyes. clear reddish yellow shades.

What We claim is:

1. Vat dyestufis of the 'anthraquinone. series corresponding to the generali'formulaf R-.-CO:NH R

It forms a red vat from which in which R stands for an anthraquinone radicle which may be substituted by a benzoylamino group and R for a 1,2-benzanthraquinone radicle in which the linkage to the CO group indicated in the formula is fixed to the Bz-nucleus,

the remaining positions of the said benzanthraquinone radicle bearing atoms selected from the group consisting of hydrogen and halogen.

2. Vat dyestufis ofv the anthraquinone series corresponding to the general formula in. whichRf stands for an anthraquinone radicle and-R for a 'l',2 -benzanthraquinone radicle in which the linkage to the -CO- group indicated in the. formula. is fixed. to the BZ-nucleus, the remaining, positions. of the said anthraquinone radicle being saturated by substitutents selected from theclass consisting of hydrogen, amino and aoylated. amino groups. and the remaining positions of the said benzanthraquinone. radicle bear. ing atoms selected from. the group. consisting of hydrogen and halogen- 3. Vat dyestuffs of the anthraquinone series.-

corresponding to. the generaliformula.

R;CO NH.-R

in which R" stands for' an anthraquinone' radicle bound in an alpha-position and R; fora 1",2-benzanthraquinone-radicl'e in which the linkage'to' the CO- group indicated in the formula is fixed to the Bz-nucl'eus; the remainingpositions of the said anthraquinone radicl'ebeing saturated by substituents selected from the class consisting of hydrogen, amino and acylated' amino groups and the remaining positions ofthe said benzanthraquinone radicle bearing atoms selected from the group-consisting of hydrogen and halogen.

5. The vat dyestuff corresponding" to the formula:

whiclrdyestufi forms. yellow needles when. crystal; lized fromi nitrobenzenetand dyes cotton yellow: shades from a yellowish'red vat.

6. The vat dyestuff corresponding to the from nitrobenzene and dyes cotton yellow shades formula: from a wine-red. vat.

' 7.'The vat dyestuff corresponding to the formula:

15 I which dyestuff dyes cotton greenish yellow shades 7 from a yellowish red vat. HEINRICH NERESHEIMER.

WILHELM RUPPEL.

20 which dyestufi crystallizes in yellow crystals ON VILSMEIER. 20

HN--C 4 (I) 0 g in Y 10 

